CN105764933B - The method for purifying polyolefin - Google Patents
The method for purifying polyolefin Download PDFInfo
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- CN105764933B CN105764933B CN201480064139.0A CN201480064139A CN105764933B CN 105764933 B CN105764933 B CN 105764933B CN 201480064139 A CN201480064139 A CN 201480064139A CN 105764933 B CN105764933 B CN 105764933B
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- density polyethylene
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 92
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 238000000746 purification Methods 0.000 claims abstract description 51
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 47
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 47
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000005977 Ethylene Substances 0.000 claims abstract description 26
- 238000012685 gas phase polymerization Methods 0.000 claims abstract description 21
- 239000011261 inert gas Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 claims description 17
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 239000012159 carrier gas Substances 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 12
- 238000005094 computer simulation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 7
- -1 polyethylene Polymers 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000009423 ventilation Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical class CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical class CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/001—Removal of residual monomers by physical means
- C08F6/005—Removal of residual monomers by physical means from solid polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/26—Treatment of polymers prepared in bulk also solid polymers or polymer melts
- C08F6/28—Purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C4/00—Treatment of rubber before vulcanisation, not provided for in groups C08C1/00 - C08C3/02
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/02—Recovery or working-up of waste materials of solvents, plasticisers or unreacted monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to the method for purifying polyolefin, the step of contact the described method includes the linear low density polyethylene for making to have synthesized by gas-phase polymerization with the purification gas comprising ethylene gas and inert gas in cleaning equipment.According to the purification process, the remaining olefinic monomer with many carbon more simply and can be removed more efficiently.
Description
Technical field
The present invention relates to the method for purifying polyolefin, and more specifically it relates to purify the method for polyolefin, this method is used
Yu Yigeng is simple and more efficient way removes the remaining olefinic monomer with high carbon number.
Technical background
With the development of the metallocene catalyst with superior catalytic activity and selectivity, widely use by being situated between in gas phase
Make olefinic polymerization in the presence of solid catalyst to prepare the industrial-scale process of polyolefin in matter.In this gas-phase polymerization process
In, alkene can be by mechanic whirl-nett reaction bed (agitated bed reactor) or by the way that reacting gas is continuously circulated so that suspension
The reaction bed fluidisation (fluidized-bed reactor) of state so as to keep reactant gas flow by polymer bed polymerize.
The polyolefin prepared by gas-phase polymerization process may include the monomers of abundant residues, and these monomers may be
Set off an explosion during the procedure of processing of product, and the property to deteriorate product may be mixed with finished product or is produced defective
Product.Therefore, it is necessary to monomer is removed from finished product.
In the past, in order to remove remaining monomer from the polyolefin prepared by gas-phase polymerization process, purification is used as by the use of nitrogen
Gas (purge gas) purifies polyolefin so that the monomer evaporation of remnants, remaining monomer is then separated, such as exist from polyolefin
In Korean Patent Publication No. 2011-0084161.
When main monomer using with the carbon atom of 4 or less in gas-phase polymerization process, remaining monomer can be with
Only pass through being separated the step of purification with nitrogen in patent described above.However, when using with 5 or more carbon atoms
When alkene is as monomer, there are such limitation：Alkene with 5 or more carbon atoms due to monomer higher boiling without
The step of only being purified by using nitrogen, removes.
Accordingly, there exist the demand of the method for exploitation purifying polyolefin, this method is suitable for using the alkene with high carbon number
The gas-phase polymerization process of monomer and being used for removes the monomer of remnants in a simpler manner.
【Prior art document】
【Patent document】
(patent document 0001) Korean Patent Publication No. 2011-0084161.
Detailed description of the invention
【Technical problem】
The method of present invention offer purifying polyolefin, this method are used to remove remnants' with simpler and more efficient way
Olefinic monomer with high carbon number.
【Technical solution】
The method that the present invention provides purifying polyolefin, this method include making synthesizing by gas phase polymerization linear low close
The step of degree polyethylene is contacted with the purification gas comprising ethylene gas and inert gas in purifying vessel.
Hereinafter, the method that the purifying polyolefin of specific embodiment according to the present invention will be described in further detail.
According to embodiment, there is provided the method for purifying polyolefin, this method include making to synthesize by gas phase polymerization
Linear low density polyethylene the step of being contacted with the purification gas comprising ethylene gas and inert gas in purifying vessel.
Present inventors have recognized that when gas phase or liquid monomer remain in polyolefin, especially by gas phase polymerization system
When in standby linear low density polyethylene, monomer may set off an explosion during the procedure of processing of product, and may be with whole production
Therefore product mixing can remove the purifying polyene of the monomer of remnants to deteriorate the property of product or produce defective product
The method of hydrocarbon is important, causes this to study.
Therefore, present inventor has performed experiment, to confirm to make the linear low density polyethylene synthesized by gas phase polymerization
Alkene can be used to evaporate with the straightforward procedure that the purification gas comprising ethylene gas and inert gas contacts in purifying vessel
The remaining monomer with removing, thereby completing the present invention.
Especially, it is not that inert gas such as nitrogen conduct is used only in the method for the purifying polyolefin of embodiment
Purification gas, but inert gas is used together in purifying vessel with ethylene gas, so as to be evaporated simultaneously in remaining monomer
Removing has 5 or more carbon atoms and high boiling alkene.Ethylene gas as purification gas is also served as linear low
Reactant in the gas-phase polymerization process of density polyethylene is recycled, so as to improve the efficiency and economy of the technique.
Linear low density polyethylene can exist as final pure linear low density polyethylene product, but can also with it is remaining
The monomer stayed in the gas-phase polymerization process of linear low density polyethylene coexists.Can with the monomer that these of gas phase or liquid phase are remaining
It can set off an explosion, and may be mixed with finished product to deteriorate the property of product, and therefore during the procedure of processing of product,
It must be driven off monomer.
As used herein, (it is gathered by the separated linea low density of purifying process to pure linear low density polyethylene
Ethene) refer to the compound comprising 99.9% or more linear low density polyethylene or generally only include linea low density
The compound of polyethylene.
Linear low density polyethylene can be selected comprising one or more free ethylene, 1- amylenes, 1- hexenes, 1- heptene,
The remaining monomer for the group that 1- octenes, 1- nonenes, 1- decene, 1- hendecenes and 1- laurylenes form.Remaining monomer it is meant that
It is remaining after gas phase polymerization to own in the monomer of the reactant of gas phase polymerization as linear low density polyethylene
Compound.
Otherwise, linear low density polyethylene can include ethene and 1- octenes.Ethene and 1- octenes are linear
The reactant monomer used in the preparation of low density polyethylene (LDPE), and ethene and 1- octenes can be in gas phase or liquid phase and linear
Low density polyethylene (LDPE) mixes.
Gross weight based on linear low density polyethylene, remaining monomer can be with by weight 0.01% to 5% amounts
By comprising.
In addition, linear low density polyethylene can pass through the gas-phase polymerization of ethene and the alkene with 3 to 10 carbon atoms
Reaction is formed.Linear low density polyethylene can be by using ethene and the alkene with 3 to 10 carbon atoms is as reactant
And by applying the equipment of agitated bed reactor, fluidized-bed reactor etc. without limitation and for gas
The method of phase-polymerization and formed, be normally used for known to the equipment and the method prepare linear low density polyethylene.
Linear low density polyethylene can have the density of 0.500g/ml to 1.000g/ml, and preferably, 0.900g/
Ml to 0.940g/ml.
Linear low density polyethylene can have the melt index (MI) (melt index) of 0.1g/10min to 100g/10min,
And preferably, 0.5g/10min to 50g/10min, as measured according to ASTM D1238.
In the method for the purifying polyolefin of embodiment, purification gas means all gas for being provided for purification
With the carrier gas that be used to provide the polyolefin prepared by gas phase polymerization to purifying vessel.
Purification gas can include being not involved in the inert gas of polymerisation and for removing the active of polymerization catalyst
Gas, and purification gas can make the remaining monomer in the linear low density polyethylene that is contained in purifying vessel continuous
Ground ventilation is they to be removed from purifying vessel, so that the vapour pressure of remaining monomer is fallen below into saturated vapour pressure,
Cause the evaporation of the monomer of remnants.
Purification gas can include ethylene gas and inert gas.The instantiation of inert gas can include helium, neon
Gas, argon gas, Krypton, xenon, radon gas, nitrogen etc., and nitrogen is preferable for easier reaction and reaction stability.
In addition, in addition to ethylene gas and inert gas, purification gas can also include high-temperature vapor, carbon monoxide
Deng.Ethylene gas and inert gas can be injected into purifying vessel individually or in the form of mixing.Especially, ethylene gas
Body is used as carrier gas, for providing the polyolefin prepared by gas phase polymerization to purifying vessel, optionally, with nitrogen
Together.
Especially, since ethylene gas has following characteristic：Its with the olefin with 5 or more carbon atoms with
Increase the saturated vapour pressure of the alkene with 5 or more carbon atoms, so as to reduce this with 5 or more carbon atoms
Alkene boiling point；Therefore it has been difficult that its evaporation, which can be evaporated, and separated when using only inert gas as purification gas
The alkene with 5 or more carbon atoms.
In pure gas, the volume ratio of ethylene gas and inert gas can be 1:99 to 70:30, and preferably, 5:
95 to 50:50.When ethylene gas is injected into purifying vessel in range above of the ethylene gas relative to the volume ratio of nitrogen
When middle, the remaining olefinic monomer with high carbon number can be separated by evaporating.
Purification gas can be injected into purifying vessel by high pressure charging pipeline.When purification gas is noted by using pipeline
When entering into purifying vessel, purification gas can with the linear low density polyethylene gathered in purifying vessel uniformly in contact with, from
And the more efficiently monomer of evaporation residue.
Purification gas can be at a temperature of 25 DEG C to 100 DEG C, and preferably, 60 DEG C to 100 DEG C.The temperature of purification gas
Spend related to the state of the evaporation of the alkene with high carbon number and linear low density polyethylene.Therefore, if temperature is less than 25 DEG C,
Alkene with high carbon number may not evaporate, and therefore linear low density polyethylene even may be remained in after purifying process
In.If temperature is higher than 100 DEG C, the linear low density polyethylene in purifying vessel is likely to be at molten state, and therefore its
Commercial value may be decreased.
Purification gas can have 1kgf/cm2To 50kgf/cm2Pressure, and preferably, 5kgf/cm2To 35kgf/
cm2.The pressure of purification gas is related to the ventilation of purification gas and the evaporation of remaining monomer.Therefore, if pressure is less than
1kgf/cm2, the ventilation of purification gas may inadequately occur.If pressure is higher than 50kgf/cm2, saturated vapour pressure reduction,
And therefore remaining monomer may be not vaporized.
Meanwhile in the method for purifying polyolefin, the step of making linear low density polyethylene be contacted with purification gas, can be with
Carry out 10 minutes to 12 it is small when.In other words, after linear low density polyethylene and purification gas are incorporated into purifying vessel,
They can be in contact with each other and react lasting 10 minutes to 12 it is small when.If time of contact is too short, one in remaining monomer
It may be not vaporized a bit, and be likely to remain in liquid.
The step of alloing linear low density polyethylene to be contacted with purification gas, carries out at a temperature of 25 DEG C to 100 DEG C.
Since Contact Temperature is related to the saturated vapour pressure of remaining monomer, the evaporation and linea low density with the alkene of high carbon number gather
The state of ethene can be according to temperature change.If Contact Temperature is less than 25 DEG C, the saturated vapour pressure in purifying vessel may mistake
It is low.In the case, it is remaining even if remaining monomer is continuously ventilated to be removed from purifying vessel by purification gas
The vapour pressure of monomer be also not reduced to less than saturated vapour pressure, and therefore, the alkene with high carbon number may be not vaporized.
In addition, if Contact Temperature is higher than 100 DEG C, the linear low density polyethylene in purifying vessel is likely to be at molten state, and
Therefore its commercial value may be decreased.
The step of alloing linear low density polyethylene to be contacted with purification gas, is in 1kgf/cm2To 50kgf/cm2Pressure
Lower progress.Contact is related to the ventilation of purification gas and the evaporation of remaining monomer.Therefore, if pressure is less than 1kgf/
cm2, the ventilation of purification gas may inadequately occur.If pressure is higher than 50kgf/cm2, saturated vapour pressure reduction, and because
This remaining monomer may be not vaporized.
Purifying vessel means space or construction (construct), wherein being prepared by gas phase polymerization linear low close
Degree polyethylene is allowed to contact with the purification gas comprising ethylene gas and inert gas.Specifically, purifying vessel has by net
Change Gas feed lines, linear low density polyethylene/carrier gas feed lines, ventilation line and pure linear low density polyethylene row
Go out the configuration of pipeline composition, and these respective components can be operated to provide purification gas, include remaining list to provide
Body and the linear low density polyethylene of carrier gas, will be shifted by evaporating separated remaining monomer and carrier gas and purification gas
To the purifier apparatus for being used to recycle and linear low density polyethylene (remaining monomer from be wherein removed) to be transferred to
For commercialized granulating process.
Meanwhile the method for purifying polyolefin can further include separation by making linear low density polyethylene be connect with purification gas
The step of gas for touching and producing.As described above, the remaining monomer being contained in linear low density polyethylene can be by making
Linear low density polyethylene is contacted and is evaporated with the purification gas comprising ethylene gas and inert gas, and the remnants evaporated
Monomer and purification gas can be separated by the single purifying process for cooling down and compressing.In addition, separated remaining list
Body and ethylene gas can be by being re-introduced into the gas-phase polymerization reactor for the preparation of linear low density polyethylene come again
Circulation.
Fig. 1 is the schematic diagram of the purifying vessel of embodiment of the present invention.
As shown in fig. 1, include being used for will be linear low comprising remaining monomer and carrier gas for the purifying vessel 6 of embodiment
Density polyethylene be transferred to purifying vessel transfer line 1, for carrier gas additionally the feeding line 2 of feed gas, be used for
4 and of discharge pipe of the feeding line 3 of feed purification gas, remaining monomer for discharging purification gas, carrier gas and evaporation
For discharging the discharge pipe 5 of pure linear low density polyethylene product.
【Beneficial effect】
According to the present invention, there is provided the method for purifying polyolefin, the method are used for simpler and more efficient side
Formula removes the remaining olefinic monomer with high carbon number.
Brief description
Fig. 1 is the schematic diagram of the purifying vessel of the method for the purifying polyolefin for embodiment.
Embodiment
Hereinafter, the present invention will be more fully described with reference to following embodiments.However, following embodiments are only used for illustration
Purpose, and the present invention is not intended to be to be restricted to such embodiments.
[embodiment 1-3]
The remaining monomer in linear low density polyolefin being introduced into purifying vessel be confirmed as ethene (C2) and
1- octenes (C8), and ethylene gas and nitrogen are injected into as carrier gas and purification gas, and then monomer and gas are mixed
Merging is kept.Then, check whether the monomer of remnants is evaporated and is separated from product.As computer simulation, Aspen is used
Plus simulation programs.Give in the following table 1 temperature and pressure and the single component specified by computer simulation into
Doses.The Computer simulation results under the conditions of corresponding are given in the following table 1.
[comparing embodiment 1]
Computer simulation is carried out under the conditions of computer simulation in the same manner as in Example 1, except not introducing ethylene gas
Outside carrier gas and purification gas, and result is provided in the following table 1.
[comparing embodiment 2]
Computer simulation is carried out under the conditions of computer simulation in the same manner as in Example 2, except not introducing ethylene gas
Outside carrier gas and purification gas, and result is provided in the following table 1.
[comparing embodiment 3]
Computer simulation is carried out under the conditions of computer simulation in the same manner as in Example 3, except not introducing ethylene gas
Outside carrier gas and purification gas, and result is provided in the following table 1.
[table 1]
1 to 4 feeding line and discharge pipe are as follows in table 1：
1. from the remaining monomer of reactor discharge
2. for the nitrogen and ethylene gas that shift and purify
3. from product and the monomer of the separated evaporation of inert gas
4. remaining liquid monomer in product and inert gas
As shown in table 1, the Computer simulation results of embodiment 1 be shown as reactant introducing all monomers be evaporated
And separation, but the result of comparing embodiment 1 is shown, liquid is kept by some 1- octenes of purifying vessel, this instruction monomer from
Product is not completely separated from, even if compared with corresponding embodiment, is not different in addition to not introducing ethene.
According to as a result, when with structure in the same manner as in Example 1 but forming not in temperature, pressure and the monomer of introducing
When the embodiment 2 and 3 carried out with the conditions of is compared with corresponding comparing embodiment 2 and 3, identical phenomenon is also observed, this is dark
Show that ethylene gas and nitrogen can additionally be used as carrier gas and purification gas to evaporate and separate the olefinic monomer with high carbon number,
Such as 1- octenes.
Claims (9)
1. a kind of method for purifying polyolefin, the described method includes the linear low density polyethylene for making to synthesize by gas phase polymerization
The step of alkene is contacted with the purification gas comprising ethylene gas and inert gas in purifying vessel,
Gross weight wherein based on the linear low density polyethylene, the linear low density polyethylene include by weight
0.01% to 5% remaining monomer,
Wherein described remaining monomer includes ethene and 1- octenes,
The step of wherein making the linear low density polyethylene be contacted with the purification gas 25 DEG C to 100 DEG C temperature and
5kgf/cm2To 35kgf/cm2Pressure under carry out.
2. the method as described in claim 1, wherein the linear low density polyethylene is by ethene and has 3 to 10 carbon originals
The gas phase polymerization of the alkene of son is formed.
3. the method as described in claim 1, wherein the linear low density polyethylene has 0.500g/ml to 1.000g/ml
Density.
4. the method as described in claim 1, wherein the linear low density polyethylene has 0.1g/10min to 100g/
The melt index (MI) of 10min.
5. the method as described in claim 1, wherein the ethylene gas described in the purification gas and the inert gas
Volume ratio is 1:99 to 70:30.
6. the method as described in claim 1, wherein the purification gas has 25 DEG C to 100 DEG C of temperature.
7. the method as described in claim 1, wherein the purification gas has 1kgf/cm2To 50kgf/cm2Pressure.
8. the method as described in claim 1, wherein making the step that the linear low density polyethylene is contacted with the purification gas
Suddenly by carry out 10 minutes to 12 it is small when.
9. the method as described in claim 1, further includes separation by making the linear low density polyethylene and the purified gas
The step of gas that body is contacted and produced.
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| KR10-2013-0147854 | 2013-11-29 | ||
| KR1020130147854A KR101534149B1 (en) | 2013-11-29 | 2013-11-29 | Method of purifying polyolefin |
| PCT/KR2014/010024 WO2015080381A1 (en) | 2013-11-29 | 2014-10-23 | Method for purifying polyolefin |
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| CN105764933A CN105764933A (en) | 2016-07-13 |
| CN105764933B true CN105764933B (en) | 2018-05-04 |
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| CN201480064139.0A Active CN105764933B (en) | 2013-11-29 | 2014-10-23 | The method for purifying polyolefin |
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| US (1) | US9790292B2 (en) |
| EP (1) | EP3075749A4 (en) |
| JP (1) | JP2016538398A (en) |
| KR (1) | KR101534149B1 (en) |
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| US11390698B2 (en) | 2017-08-01 | 2022-07-19 | Exxonmobil Chemical Patents Inc. | Methods of polyolefin solids recovery |
| CN111148771B (en) * | 2017-08-01 | 2023-07-18 | 埃克森美孚化学专利公司 | Process for recovery of polyolefin solids |
| CN114014960B (en) * | 2021-10-21 | 2023-07-11 | 金聚合科技(宁波)有限公司 | System and method for polyolefin purification |
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| JPS6079017A (en) * | 1983-10-05 | 1985-05-04 | Chisso Corp | Recovery of unreacted olefin remaining in polyolefin powder |
| US5376742A (en) * | 1993-09-23 | 1994-12-27 | Quantum Chemical Corporation | Monomer recovery in gas phase fluid bed olefin polymerization |
| CN101501079A (en) * | 2006-08-03 | 2009-08-05 | 巴塞尔聚烯烃股份有限公司 | Process for the polyolefin finishing |
| CN103298842A (en) * | 2010-12-17 | 2013-09-11 | 尤尼威蒂恩技术有限责任公司 | Systems and methods for recovering hydrocarbons from a polyolefin purge gas product |
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| US4372758A (en) * | 1980-09-02 | 1983-02-08 | Union Carbide Corporation | Degassing process for removing unpolymerized monomers from olefin polymers |
| JPH0439305A (en) * | 1990-06-04 | 1992-02-10 | Mitsubishi Petrochem Co Ltd | Method for treating resin in purge container |
| JP3162241B2 (en) * | 1994-01-18 | 2001-04-25 | 株式会社日立ビルシステム | Elevator abnormal data collection device |
| US5521264A (en) * | 1995-03-03 | 1996-05-28 | Advanced Extraction Technologies, Inc. | Gas phase olefin polymerization process with recovery of monomers from reactor vent gas by absorption |
| GB9622715D0 (en) * | 1996-10-31 | 1997-01-08 | Bp Chem Int Ltd | Nozzle |
| JP2004204028A (en) | 2002-12-25 | 2004-07-22 | Sumitomo Chem Co Ltd | Polyolefin vapor phase polymerization process |
| WO2004092228A1 (en) | 2003-04-17 | 2004-10-28 | Basell Poliolefine Italia S.R.L. | Gas-phase olefin polymerization process |
| EP2083020A1 (en) | 2008-01-18 | 2009-07-29 | Total Petrochemicals Research Feluy | Process for monomer recovery from a polymerization process |
| EP2172495A1 (en) | 2008-10-03 | 2010-04-07 | Ineos Europe Limited | Method for the production of polymers |
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2013
- 2013-11-29 KR KR1020130147854A patent/KR101534149B1/en active IP Right Grant
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- 2014-10-23 EP EP14866065.7A patent/EP3075749A4/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6079017A (en) * | 1983-10-05 | 1985-05-04 | Chisso Corp | Recovery of unreacted olefin remaining in polyolefin powder |
| US5376742A (en) * | 1993-09-23 | 1994-12-27 | Quantum Chemical Corporation | Monomer recovery in gas phase fluid bed olefin polymerization |
| CN101501079A (en) * | 2006-08-03 | 2009-08-05 | 巴塞尔聚烯烃股份有限公司 | Process for the polyolefin finishing |
| CN103298842A (en) * | 2010-12-17 | 2013-09-11 | 尤尼威蒂恩技术有限责任公司 | Systems and methods for recovering hydrocarbons from a polyolefin purge gas product |
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| KR101534149B1 (en) | 2015-07-03 |
| US20160289347A1 (en) | 2016-10-06 |
| KR20150062819A (en) | 2015-06-08 |
| US9790292B2 (en) | 2017-10-17 |
| EP3075749A1 (en) | 2016-10-05 |
| WO2015080381A1 (en) | 2015-06-04 |
| JP2016538398A (en) | 2016-12-08 |
| CN105764933A (en) | 2016-07-13 |
| EP3075749A4 (en) | 2017-06-28 |
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